US3919263A - Process for the preparation of anthraquinone - Google Patents
Process for the preparation of anthraquinone Download PDFInfo
- Publication number
- US3919263A US3919263A US468139A US46813974A US3919263A US 3919263 A US3919263 A US 3919263A US 468139 A US468139 A US 468139A US 46813974 A US46813974 A US 46813974A US 3919263 A US3919263 A US 3919263A
- Authority
- US
- United States
- Prior art keywords
- process according
- anthracene
- halide
- oxygen
- activator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 8
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title abstract description 23
- 150000004056 anthraquinones Chemical class 0.000 title abstract description 23
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 81
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- -1 iron halide Chemical class 0.000 claims description 23
- 239000012190 activator Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical group NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229940093476 ethylene glycol Drugs 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- KULLJOPUZUWTMF-UHFFFAOYSA-N 9-chloroanthracene Chemical compound C1=CC=C2C(Cl)=C(C=CC=C3)C3=CC2=C1 KULLJOPUZUWTMF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 9-bromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=CC2=C1 ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- CQXADFVORZEARL-UHFFFAOYSA-N Rilmenidine Chemical compound C1CC1C(C1CC1)NC1=NCCO1 CQXADFVORZEARL-UHFFFAOYSA-N 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- XMWJLKOCNKJERQ-UHFFFAOYSA-N 1-bromoanthracene Chemical compound C1=CC=C2C=C3C(Br)=CC=CC3=CC2=C1 XMWJLKOCNKJERQ-UHFFFAOYSA-N 0.000 description 1
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- JDFDHBSESGTDAL-UHFFFAOYSA-N 3-methoxypropan-1-ol Chemical compound COCCCO JDFDHBSESGTDAL-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- QLRRUWXMMVXORS-UHFFFAOYSA-N Augustine Natural products C12=CC=3OCOC=3C=C2CN2C3CC(OC)C4OC4C31CC2 QLRRUWXMMVXORS-UHFFFAOYSA-N 0.000 description 1
- 101100243951 Caenorhabditis elegans pie-1 gene Proteins 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- JMBNQWNFNACVCB-UHFFFAOYSA-N arsenic tribromide Chemical compound Br[As](Br)Br JMBNQWNFNACVCB-UHFFFAOYSA-N 0.000 description 1
- 229940077468 arsenic tribromide Drugs 0.000 description 1
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 description 1
- IKIBSPLDJGAHPX-UHFFFAOYSA-N arsenic triiodide Chemical compound I[As](I)I IKIBSPLDJGAHPX-UHFFFAOYSA-N 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- ZFYHTGWRVARNFD-UHFFFAOYSA-I pentaiodo-lambda5-stibane Chemical compound I[Sb](I)(I)(I)I ZFYHTGWRVARNFD-UHFFFAOYSA-I 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- UFHHEWUNBJORRL-UHFFFAOYSA-J tetrachlorobismuth Chemical compound Cl[Bi](Cl)(Cl)Cl UFHHEWUNBJORRL-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
Definitions
- Anthraquinone is a compound of great industrial value, particularly in the manufacture of dyestuffs.
- Various processes for the preparation of anthraquinone have been proposed, especially from phthalic anhydride (condensation with benzene in the presence of anhydrous aluminium chloride to form benzoylbenzoic acid which is converted to anthraquinone with sulphuric acid).
- anthraquinone by oxidation of anthracene in the liquid phase by means of oxygen or an oxygen-containing gas in the presence of an inert organic diluent and in the presence of cupric bromide.
- cupric chloride makes it possible to alter the course of the reaction so that anthraquinone is the preponderant product and, in some cases, depending on the solvent used, so that anthraquinone is practically the only product, the formation of 9- bromoanthracene being very slight and non existant.
- diluents which are particularly suitable are linear or branched saturated aliphatic alcohols containing 1 to 10 carbon atoms, and compounds of the general formula:
- R and R which may be identical or different, denote a hydrogen atom or a linear or branched alkyl radical containing 1 to carbon atoms, R denotes a linear or branched alkylene radical containing l to car bon atoms and n is an integer from up to 3.
- R and R can be, for example, a methyl, ethyl or propyl radical and R can be, for exam ple, an ethylene, propylene, tetramethylene, pentamethylene, hexamethylene or octamethylene radical.
- diluents which may be used include methanol, ethanol, propanol, isopropanol, lbutanol, isoamyl alcohol, tertiary amyl alcohol, n-pentanol, l-hexanol, the octanols, ethylene glycol, 2- methoxyethanol, 1,2-dimethoxy-ethane, propane-l ,2- diol, propane-l,3-diol, 3-methoxyl-propanol, 1,3- dimethoxy-propane, 2-methyl-propane-l,3diol, 2,2- dimethyl-propanel ,3-diol, butane-1,4-diol, butane- 2,3-diol, pentane-l,5--diol, hexane-1,6-diol, diethylene glycol, dipropylene glycol, tripropylene glycol and 1,5
- non-condensed glycols are preferred.
- cupric bromide and an aliphatic glycol, especially ethylene glycol makes it possible to obtain excellent yields of anthraquinone.
- reaction mixture it is, of course, possible to use a mixture of 2 or more organic diluents; it is also possible for the reaction mixture to contain water.
- activators namely inorganic acids
- hydrochloric acid iron halides (chlorides, bromides, fluorides and iodides), aluminium halides and halides of elements from Groups 3A, 4A and 5A of the Periodic Table as given in Handbook of Chemistry and Physics, 45th edition, 1964, Physics", page B-2.
- activators namely inorganic acids
- hydrochloric acid iron halides (chlorides, bromides, fluorides and iodides)
- aluminium halides and halides of elements from Groups 3A, 4A and 5A of the Periodic Table as given in Handbook of Chemistry and Physics, 45th edition, 1964, Physics", page B-2.
- Acids which have a pK in aqueous solution of less than 2, and preferably of at most 1, are the inorganic acids which may be used, for example sulphuric acid, perchloric acid, pyrophosphoric acid and hydrobromic acid.
- Hydrobromic acid is particularly suitable, both because of its effect on the reaction rate and because of the fact that an anion which is already present in the medium is used.
- ferrous and ferric chlorides ferrous and ferric bromides, aluminium chloride, aluminium bromide, aluminium fluoride, boron trifluoride, antimony pentachloride, antimony trichloride, antimony tribromide, antimony trifluoride and pentafluoride, antimony pentaiodide, arsenic tribromide, arsenic trichloride, arsenic pentafluoride, arsenic trifluoride, arsenic triiodide and pentaiodide, and bismuth tetrachloride and trichloride.
- those of antimony generally produce the most pronounced effect on the kinetics of the oxidation reaction, so that they form a preferred class of activators.
- cupric bromide Although it is preferable, for reasons of convenience, to employ cupric bromide directly, it is possible to form it in situ from cuprous bromide.
- cupric bromide expressed in mols per mol of anthracene, can vary within wide limits. Thus, for example, it can be at least l A 10 and can be as much as 2 mols per mol of anthracene. The latter value can be exceeded but, in general, it is not necessary to exceed l mol of cupric bromide per mol of anthracene.
- the quantity of activator which may be present, can also vary within wide limits, depending on the nature of the compound employed. In general terms, it can be at least 1 10 mol and can be as much as 10 mols per mol of anthracene; however, in the case of antimony halides, it is generally not necessary to exceed l mol per mol of anthracene.
- the temperature at which the reaction is carried out suitably varises from 20 to 200C.
- a temperature of from 20 to C is generally very suitable.
- the oxidation is suitably carried out under a partial pressure of 3 oxygen of 0. l to 20 bars.
- the diluent or the activator such as boron trifluoride, arsenic trifluoride or arsenic pentafluoride, is gaseous at the chosen temperature, it is preferable to work under pressure.
- the contents of The process according to the present invention is the flask are heated at 80C for 8 hours and then cooled particularly simple to effect on a technical scale and to 20C, and the reaction mixture is treated as in Examcan be carried out continuously.
- pie 1. Anthracene (15.2% by weight of the anthracene The following Examples further illustrate the present introduced), 9-chloro-anthracene representing 38.6% invention. of the anthracene introduced and anthraquinone representing 36% of the anthracene introduced are mea- EXAMPLE 1 sured in the precipitate obtained.
- Example 16 The experiment of Example 2 is repeated, and then. at the end of the reaction, the filtrate is recovered and is introduced into the apparatus described in Example I, 0.4 cm of hydrobromic acid and 7.12 g of anthracene are added and the whole is heated at 82C for 8 hours. After treatment as in Example l, 7.32 g of a product containing 81.5% of the anthracene introduced and anthraquinone corresponding to 17% of the hydrocarbon introduced (corresponding to a yield of 92% relative to the converted anthracene) are recovered.
- R and R which may be identical or different. denote a hydrogen atom or a linear or branched alkyl radical containing up to 5 carbon atoms, R denotes a linear or branched alkylene radical containing up to ID carbon atoms, and n is an integer from 1 to 3.
- cupric bromide is present in an amount of at least I A l0 mol per mol of anthracene.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7317155A FR2228755B1 (enrdf_load_html_response) | 1973-05-11 | 1973-05-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3919263A true US3919263A (en) | 1975-11-11 |
Family
ID=9119197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US468139A Expired - Lifetime US3919263A (en) | 1973-05-11 | 1974-05-08 | Process for the preparation of anthraquinone |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3919263A (enrdf_load_html_response) |
| JP (1) | JPS5018454A (enrdf_load_html_response) |
| BE (1) | BE814878A (enrdf_load_html_response) |
| DE (1) | DE2422461A1 (enrdf_load_html_response) |
| FR (1) | FR2228755B1 (enrdf_load_html_response) |
| GB (1) | GB1433566A (enrdf_load_html_response) |
| NL (1) | NL7405997A (enrdf_load_html_response) |
| PL (1) | PL88778B1 (enrdf_load_html_response) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5647260B2 (enrdf_load_html_response) * | 1973-05-29 | 1981-11-09 | ||
| JPS53118230A (en) * | 1977-03-26 | 1978-10-16 | Shinko Wire Co Ltd | Preparation of metal covered wire |
| DE4319569C1 (de) * | 1993-06-08 | 1994-06-16 | Mannesmann Ag | Verfahren und Vorrichtung zur Erzeugung von Halbzeug |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1787416A (en) * | 1916-06-22 | 1930-12-30 | Ig Farbenindustrie Ag | Catalytic oxidation of organic compounds |
| US1787417A (en) * | 1921-08-11 | 1930-12-30 | Ig Farbenindustrie Ag | Catalytic oxidation of organic compounds |
| US1880322A (en) * | 1928-08-23 | 1932-10-04 | Selden Res & Engineering Corp | Production of non-acidic carbonyl compounds |
| US2643269A (en) * | 1950-07-18 | 1953-06-23 | Socony Vacuum Oil Co Inc | Halogen-promoted oxidation |
| US2824881A (en) * | 1954-04-05 | 1958-02-25 | Ciba Ltd | Process for the manufacture of anthraquinone by oxidation of anthracene |
-
1973
- 1973-05-11 FR FR7317155A patent/FR2228755B1/fr not_active Expired
-
1974
- 1974-05-03 NL NL7405997A patent/NL7405997A/xx not_active Application Discontinuation
- 1974-05-08 JP JP49050332A patent/JPS5018454A/ja active Pending
- 1974-05-08 US US468139A patent/US3919263A/en not_active Expired - Lifetime
- 1974-05-09 DE DE2422461A patent/DE2422461A1/de active Pending
- 1974-05-10 BE BE144199A patent/BE814878A/xx unknown
- 1974-05-10 GB GB2081074A patent/GB1433566A/en not_active Expired
- 1974-05-11 PL PL1974171004A patent/PL88778B1/pl unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1787416A (en) * | 1916-06-22 | 1930-12-30 | Ig Farbenindustrie Ag | Catalytic oxidation of organic compounds |
| US1787417A (en) * | 1921-08-11 | 1930-12-30 | Ig Farbenindustrie Ag | Catalytic oxidation of organic compounds |
| US1880322A (en) * | 1928-08-23 | 1932-10-04 | Selden Res & Engineering Corp | Production of non-acidic carbonyl compounds |
| US2643269A (en) * | 1950-07-18 | 1953-06-23 | Socony Vacuum Oil Co Inc | Halogen-promoted oxidation |
| US2824881A (en) * | 1954-04-05 | 1958-02-25 | Ciba Ltd | Process for the manufacture of anthraquinone by oxidation of anthracene |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7405997A (enrdf_load_html_response) | 1974-11-13 |
| GB1433566A (en) | 1976-04-28 |
| DE2422461A1 (de) | 1974-11-28 |
| BE814878A (fr) | 1974-11-12 |
| FR2228755B1 (enrdf_load_html_response) | 1975-11-21 |
| JPS5018454A (enrdf_load_html_response) | 1975-02-26 |
| FR2228755A1 (enrdf_load_html_response) | 1974-12-06 |
| PL88778B1 (enrdf_load_html_response) | 1976-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0118851B1 (en) | Process for producing a chlorohalobenzene | |
| KR900003295B1 (ko) | 할로겐화 핵치환 벤젠류의 제조방법 | |
| US3919263A (en) | Process for the preparation of anthraquinone | |
| US3151051A (en) | Synthesis of fluorine compounds | |
| US3922290A (en) | Process for the preparation of anthraquinone | |
| Kovacic et al. | Reactions of Molybdenum Pentachloride and Vanadium Tetrachloride with Alkyl-and Halobenzenes1 | |
| US3794668A (en) | Vapor phase oxidation of phenols | |
| US4312811A (en) | Process for the production of substituted anthraquinones | |
| US3256343A (en) | Production of halogen derivatives | |
| US3148222A (en) | Oxychlorination of benzene in the presence of cucl2/licl catalysts | |
| US2608591A (en) | Substitution chlorination of aromatic compounds with liquid chlorine | |
| US3996274A (en) | Method for producing chlorobenzoyl chloride | |
| US3931254A (en) | Process for the preparation of anthraquinone | |
| Duke et al. | ACID-BASE REACTIONS IN FUSED SALTS. THE DICHROMATE-BROMATE REACTION1 | |
| EP0167153B1 (en) | Process for the preparation of 2,3,5-trimethylbenzoquinone | |
| US1919886A (en) | Process for adding hydrogen halide to acetylene | |
| US4079090A (en) | Preparation of trichloromethyl-trifluoro methyl-benzenes | |
| Sawaguchi et al. | Preparation of aromatic fluorides: facile photo-induced fluorinative decomposition of arenediazonium salts and their related compounds using pyridine–nHF | |
| US3801626A (en) | Process for the production of dichloroacetoxypropane | |
| US5736012A (en) | Process for the preparation of a fluorinated acid | |
| US4214100A (en) | Process for preventing blackening of phthalic acid | |
| CA1128962A (en) | Process for the manufacture of 1,3,5-trichlorobenzene | |
| Husted et al. | The Chemistry of the Perfluoroaliphatic Acids and their Derivatives. VI. The Hofmann Reaction1 | |
| US2993937A (en) | Fluorination of aromatic compounds | |
| US3634520A (en) | Nitration of aromatic ring-containing compositions |